Cooczhs



F at enter] Jan. 2, 1943 FFlE TALLIFEROUS AZO-DYESTUFFS CON- I TAENKNG THE PYRAZDLONE RUG Max Schmidt, Riehen, Switzerland, assignor to the firm Society of Chemical industry in Basle,

Basel, Switserland No Drawing. Application May 18, 1938, Serial No. 208,704. In Switzerland May. 22, 1937 4 Claims.

According to this invention new metalliferous azo-dyestufis containing the pyrazolone ring which are distinguished by excellentvproperties of fastn'ess and especially by the high fastness to light of their dyeings on cotton are made by "causing a halide of a polyvalent organic acid or an analogue thereof to react with a coupling component which, on the one hand, is capable of being combined with diam-compounds to form azo-dyestuffs owing to the presence of a 5-py- *razolone ring and, on the other hand, contains an aromatically bound amino'-group, and causing the product so obtained to react with 'a diazocompound which is substituted in ortho-position to the diazo-group by a group which is capable of forming complex metal compounds in combination with the enolisable (JO-group of the py razolone, for example a hydroxyl or carboxyl group, or by a substituent capable of being converted into such a group, and converting the dyestufi so obtained into a complex metal compound.

Like dyestufis are also obtained by causing a diazo-compound of the kind above defined to 5 react in a first stage with a coupling component which, on the one hand, is capable of combining with diam-compounds to form azo-dyestuffs, owing to the presence of a 5-pyrazolone ring, and, on the other hand, contains an aromatically abound amino-group or a group capable of con- .version into such an amino-group, and in a sec- 1 0nd stage causing to act on the dyestuff so ob- "tained in any desired order of succession an agent yielding metal and a halideoi a polyvalent acid or an analogue thereof, if required after conversion into anaromatically bound aminogroup of the group capable of conversion into such a group.

The procedure may also be such that the metallization is combined with the production of the azo-dyestufi or that during the metallization the substituent in ortho-position to the chasmgroup of the diazotization component which is capable of conversion into a hydroxyl or carboxyl group, for example a methoxy-group, a halogen ,atom or a carboxylic ester group, is converted into the hydroxyl or carboxyl group. Alternatively, the metallization may occur only during the use of the dyestufi, for example during the dyeing or on the fibre.

The dyestufis may be metallized by treatment with a salt, oxide, or hydroxide of a metal capable .of yielding complex compounds with mordant -;dyestufis, such as a salt of copper, nickel, cobalt,

'Lsiron, chromium, manganese or the like."

, formula (Ci. milk-147) Among the diam-components which may be used for making the new azo-dyestuffs there may be mentioned above. all l-aminobenzene-2-carboxylic acid, 1-aminobenaene l-nitro2-carboxylic acid, 1-aminobenzenei-sulfo-2-carboxylic, l-arnino l chloro-Z-hydroxybenzene, l-aminoi-riitro-2 hydroxybenzene, l-amino-2-hydroxybenzene -sulfonic acid, l-amino 2 chlorbenzene 4 sulionic acid, l-amino-"Z-methoxybenzenel-sulionic acid, l-arnino 2 hydroxynaph-' thalene' l sulfonic acid, Z-amino l hydroxynaphthalene -l :8 disulfonic acid; furthermore, l-amino-Z-chlcrcor 1-amino 2 methoxybenzene-5-sulionicacid and so on. Among the coupling components which may be used for making the new dyestuffs there may be mentioned the 'ureas or thioureas from amino-arylpyrazolones,

for example'the urea from l-( l amino) -phenyl- 5-pyrazolone-3carboxylic acid and phosgene, or the condensation products from amino-arylpyrazolones and heterocyclic compounds containing replaceable halogen atoms, such as 'cyanuric chloride, for example the ternary condensation product from 1 mol of cyanuric chloride, 2 mols of l- (4' -amino) phenyl 5-pyrazolone-3-carboxy'lic acid and 1 mol of aniline.

In making the azo-dyestufis I in accordance with the invention by first preparing the simple azo-dyestuffs and converting it into a urea derivative or into an analogous compound, such as a triazine derivative, there are used as coupling components aminophenylpyrazolones or the corresponding nitro-compounds; In the latwherein Rrand R2 are'aromatic nuclei selected from the group consisting of benzeneand naph- Nal;l.

wherein a stands for a member of the group consisting of the carbonyl group anda triazine nucleus and wherein the -III groups are not linked in 2'-position to the phenyl radi-- COOH N/ l O HOaS N- cals standing in l-position to the pyrazolone nuclei, which products are yellow to brown powders dyeing the fiber fast yellow to orange and brown tints.

The following examples illustrate the invention the parts being by weight:

Example 1 23.2 parts of the urea from 1-(4-amino)- phenyl-3-methyl-5-pyrazolone are dissolved in 3000 parts of water with the addition of 170 parts of anhydrous sodium carbonate and 40 parts of sodium hydroxide. There is then added in the cold a diazo suspension prepared from 21.7 parts of 1-amino4-sulfobenzene 2 carboxylic acid. After the whole has been stirred for a long time the dyestuif of the formula Example 2 21.9 parts of 1-(4-amino)-phenyl-5-pyrazolone-3-carboxylic acid are dissolved in 3000 parts of water with the addition of 1'70 parts of anhydrous sodium carbonate or 140 parts of sodium hydroxide and 150 parts of crystallized sodium acetate. The solution is cooled with ice and mixed with a diazo solution. prepared from 21.7 parts of l-amino-4-sulfobenzene-2-carboxylic acid; The dyestufi formed is precipitated with the aid of sodium chloride and dissolved in 1000 parts of water together with 200 parts of anhydrous sodium carbonate, and the solution is treated with phosgene until a sample can no longer be diazotized. The dyestufi of the formula COOH COOH

is precipitated by the addition of common salt and is converted in the manner indicated in Example 1 into a copper compound which is similar to that described in Example 1.

The substitution of the 6-nitro-2-aminophenol-4-sulfonic acid for the 1-amino-4-sulfobenzene-Z-carboxylic acid leads to a dyestufi" whose copper, nickel and cobalt compounds dye cotton brown tints.

Example 3 55 parts of the secondary condensation product from 1 mol of cyanuric chloride and 2 mole of 1- (3'-amino) -phenyl-5 pyrazolone 3 carboxylic acid are introduced into a mixture of 200 parts of water and 50 parts of anhydrous sodium carbonate. After addition of some ice the COOH Ill H0 is separated by filtering and introduced into about 500 parts of hot water. A solution from 28 parts of crystallised copper sulfate in about 60 parts of aqueous ammonia of per cent strength is then addedand the whole is heated for some is conducted in presence of the copper compound or if the isomeric 3-aminopyrazolone is used as parent material.

whole is mixed with a diazo suspension prepared in the usual manner from 43.4 parts of 1- amino-4-sulfobenzene-2-carboxylic acid. The whole is stirred for some time and the dyestuff formed of the formula COOH N N=( J MH N 1100B is isolated by addition of common salt and illtered. It is converted in the manner indicated in Example 1 into its copper compound, which dyes cotton or viscose artificial silk yellow shades fast to light. The isomeric dyestuff from the (4'-amino)-pheny1-pyrazolone produces similar dyeings on cotton. The dyestuifs from such condensation products'in which the last chlorine atom of the cyanuric chloride is replaced by ammonia, mon-omethylamine, aniline, ortho-toluidine, l-aminobenzene-l-sulfonic acid, p-na'phthylamine and the like behave analogously; If

aim 1-(3'-amino) phenyl-S-pyrazolone-3-carboxylic the "condensation product contains a sufficient number of groups lending solubility, th'el-amino- 4-sulfcbenzene-2-carboxylic acid can also be replaced by the 1-aminobenzene-z-carboxylic acid. 5 The following are formulas of such dyestufis The same or similar dyestufis are 'turther obtained by causing 1 mol of cyanuric chloride to react with 2 mols of the azo-dyestufi from acid or 1-(4'-amino) -phenyl-3-methyl-5-pyrazolone and diazotized 1-amino-4-sulfobenzene-2- carboxylic acid and converting the resulting dyestufisinto its copper compound; if necessary after reaction of the last chlorine atom withan aminocompound named in the preceding paragraph.

If instead of sulfoanthranillcacid or the an- "What 'I claim-is:- 1. The-metal compounds of the general formula of the 'azo dyestufis wherein R1 and R2 are mono-cyclic aromatic. nuclei of thelhenzene series: containing a COOH group standing in ortho-position to the -N=N- group, a: and t stand for members of the group consisting of H, CH3, COOH, COOC2H5 g COOH and phenyl, and 2 stands for a connecting member of the formula wherein a stands for a member of the group consisting of the carbonyl group and a triazine compound. and wherein the groups are linked in a position difierent from the 2'-position to the phenyl radicals standing in 1- position to the pyrazolone nuclei, which products: are yellow to brown powders dyeing the fiber fast yellow tints.

2. The copper compounds of the azo-dyestufisof the general formula wherein R1 and R2 are mono-cyclic aromatic nuclei of the benzene series containing a COOH group standing in ortho-positiontothe N=N-- group, a: and t stand for members of the group consisting of H, CH3, COOH, COOCzHs and r are yellow to brown wherein y stands for a member selected from the? group consisting of H and SOsH, a: and t stand for members of the group consisting of H, CH3, COOH, COOC2H5 and phenyl, and 2 stands for a connecting member of the formula NaN- I I H H wherein a. stands for, a.- member of the group groupland a triazine consisting of' the carbonyl compound and wherein the LQTL;

groups are linked in a position different from the 2'-position to the phenyl radicals standing in 1- position to the pyrazolone nuclei, which products are yellow powders dyeing the fiber yellow tints. 4. The copper compounds of the azo-dyestufis of the general formula wherein :1 stands for a member selected from the group consisting of H and SO3H and 2 stands or aconnectingmember of the formula r r- H H wherein a 'stands' for a member of the "group consisting of the carbonyl group and a triazine compound, which products are yellow dyeing the-fiber last yellow tints.

sent/m).

member of the group powders 

